Continuous water analyzer



8, 1947- R. L. TUVE ET AL CONTINUOUS WATER ANALYZER Filed Dec. 8, 1942 3 Sheets-Sheet l 3 wu Mu karma EE U p w\ gm HO F; 3 6 R 3 Sheets-Sheet 2 Filed Dec. 8, 1942 OUT RICHARD L.,TUVE

' JOSEPHC.WHITE. ELMER L.LUKE I MZLQ Nov. 18, 1947.

R. L. TUVE ETAL CONTINUOUS WA TER ANALYZER Filed Dec. 8, 1942 3 Sheets-Sheet 3 RICHARD L. T-UVE v. 7 8 x: N8 1359:

JOSEPH 0 WHITE I ELMER L. LUKE Patented Nov. 18, 1947 CONTINUOUS WATER ANALYZER Richard L. Tuve, Silver Spring, and Joseph C. White, University Park, Md., and Elmer L. Luke, Washington, D. 0.

Application December 8, 1942, Serial No. 468,250

1 Claim. (01. 23--255) (Granted under the act of March 3, 1883, as

amended April 30, 1928; 370 O. G. 757) This invention relates to methods for the continuous analysis of water, and to improved apparatus therefor. In particular the invention is directed to the continuous analysis of water for The method and apparatus of this invention are described in connection with oxygen determination, with reference to the accompanying drawing in which:

dissolved oxygen. 5 Fig. 1 is a schematic diagram showing the flow Due to the corrosive properties of dissolved cxyof water and reagents through the apparatus and gen in water used in steam generators, because of the relative placement of parts and their functhe high temperatures involved, it is highly detions; sirable to be able to determine the concentration Fig. 2 is a detailed View of the absorption cells of oxygen in the feedwater even when present in I5 and 33 of Fig.,1, shown in cross section; exceedingly minute amounts. Also it is neces- Fig. 3 is a detailed cross sectional view of the sary, from a practical standpoint, to make the deelectrolysis cell 24 of Fig. 1; and termination easily and quickly, and a continuous Fig. 4 is a detailed viewof the pu ps 22 and analysis system is preferred. 30 of Fig. 1.

Several methods of such continuous analysis Referring to Fig. 1, the Water to be analyzed is have been proposed, and one of the best involves ad t h app through n inlet V v the determination of dissolved oxygen by coloril0 and passes t ugh a second valve ll into a metric means. For example the water is passed fl Wmet r l2- B twe t valves and II is in series through two color absorption tubes of a standard overflow standpipe l3 which is op at identical size, the amount of light absorbed being the upper y m ans o the Valve 1 l and the determined by illuminating the cells at one end and observing the transmitted light by means of a pair of photocells, or other light responsive elements at the other end. As the water passes from the first cell to the second a mixture of caustic and pyrogallol solutions is added. Due to the oxygen-sensitiveness of the alkaline pyrogallol and the coloring properties of the oxidized product, the light absorbed in the second cell will exceed that absorbed in the first cell in accordtance with the concentration of dissolved oxygen in the water.

As heretofore proposed, the above method has had several disadvantages which have limited its commercial use. For one thing the oxygen concentrations being measured are so small (0.1 to 0,0001% by volume) that accurate colorimetric measurement is imperative. This involves accurate calibration of the apparatus employed and reproducible results.

This invention provides an improved apparatus for conducting the above described analyses quickly and accurately. The apparatus is easily calibrated by a special method herein disclosed and the calibration checked whenever desired. The invention also provides specially designed absorption cells for continuous fluid flow, an electrolysis cell for calibration, and metering pumps particularly designed for handling the reagents involved. In addition to oxygen determination, the apparatus is equally suited to the continuous determination of other substances by colorimetric means. For example, iron may be colorimetricallyv determined by means of the thiocyanate, and pH canbe determined by indicators.

reading of the flowmeter 12 the flow of water through the apparatus is adjusted to the desired rate. From the flowmeter I 2 the water passes through a conduit M to an absorption cell [5 having glass ends. In theabsorption cell l5 the color or light transmittanceof the water is measured to provide a zero setting or datum line for subsequent analysis measurements, all as described further onf From the cell I5 the water passes through a conduit l6 into a mixing coil l1 which is made of capillary tubing (the sharp bends providing turbulent flow) simultaneously with a metered amount of potassium hydroxide, or caustic, solution from a conduit [8 which joins the conduit l6.

The potassium hydroxidesolution is stored in a reservoir l9 from which it is supplied through a conduit 20 and shut ofi valve 2| to a metering pump 22, thedischarge of which is connected to the conduit l8. A drain valve 23 is connected to the conduit 20 for cleaning purposes.

In the mixing coil [1 the water and potassium hydroxide solution are thoroughly mixed and then are passed through an electrolysis cell 2d (not-used during analysis) into asecond mixing coil 25 similar in construction to the capillary coil ll. In the mixing coil 25 the water and potassium hydroxide are mixed with a specially prepared solution of pyrogallol from a conduit 1 2B which joins the mixing coil 25.

A drain valve 3| is connected to the conduit 28 for cleaning purposes.

In the mixing coil 25 the pyrog-allol is brought into intimate contact with the entire sample of water being analyzed, under alkaline conditions, and is oxidized by all dissolved oxygen in the water. As the oxidation product is very dark in color the mixture passing from the mixing coil 25 has acquired a darker shade, the intensity of which depends on the concentration of dissolved oxygen in the water being analyzed. From the mixing coil 25 the darkened mixture passes into a ballast tank 32 to smooth out the flow and then, via a conduit 34, into a second absorption cell 33 which is identical in construction to the cell l5. From the absorption cell 33 the liquid passes out of the apparatus through a drain conduit 35.

Since th treated water continuously passing through the cell 33 is darker than the untreated water passing through the cell l in relation to the concentration of dissolved oxygen in the water, a colorimetric comparison of the liquids in the cells l5 and 33 will indicate the percent oxygen in the water. This is done by photoelectric means.

A source of light 36, supplied by a constant wattage transformer 31 to minimize the effect of voltage fluctuations, is mounted on a swivel 33 so that it may be positioned at the end of either of the absorption cells I5 and 33 to direct a steady beam of light therethrough. The source of light 36 may be of any type, one very satisfactory arrangement being an automobile headlight, condensing lenses to form a beam and an iris diaphragm 39 to control the intensity of the beam. At the other ends of the absorption cells l5 and 33 a photoelectric .cell 40 is mounted on a swivel 4| which is connected to the swivel 33 by means of a rod 42 so that movement of the rod or either swivel simultaneously positions the source of light 36 and the photocell 4!] at the ends of the same absorption cell. In this way either cell may be quickly examined by the photocell 40 under comparative conditions. The photocell 40 may be either the high vacuum type which changes resistance with incident light or it may be the photovoltaic type. In Fig. 1 the photocell 40 is of th latter kind, so that the reading is obtained by a microammeter 43 connected in series therewith. In order that the photocell may cover a practical range it is desirable to filter out the end portions of the spectrum, and for this purpose a filter 44 is positioned in front of the photocell 40 and is mounted on it.

In order to operate be'apparatus it is necessary to calibrate it against water having known oxygen concentrations. This is done by admitting oxygen-free water into the inlet valve l0 and passing it throughthe apparatus with the reagents as described. The water used for the calibration may be freed of oxygen by distillation and de-aeration in conventional manner. The water should be checked for presence of oxygen by means of a Winkler analysis, so that if there is any residual trace it may be taken into account in the calibration. After establishing uniform flow of the oxygen-free water through the apparatus at the rate offlow desired the light source is turned on'and the light adjusted to give a maximum reading on the meter 43 when the photocell is receiving the light through the cell l5. Then the cell 33 is examined and the difierence in reading between the twocells noted. The reading for the cell 33 will be less 4 than that of the cell l5 due to light absorption by the pyrogallol, which depends on the residual oxygen in the water, and the difierence in readings is the first point on the calibration curve, as the residual oxygen, if any, is known from the Winkler analysis.

Succeeding points on the calibration curve are obtained by introducing various known amounts of oxygen continuously into the water. This is accomplished by the electrolysis cell 24. By passing a current of known magnitude through the cell the rate of evolution of oxygen at the anode is determined, and as th rate of flow of liquid through the cell is known from the reading of the flowmeter l2 and the speeds of the pumps 22 and 30 are constant for all analyses, the oxygen concentration in the water leaving the cell 24 is known. Thus any desired number of check points may be obtained and a calibration curve of the apparatus drawn. Since the oxygen concentrations measured are extremely small, usually a fraction of a percent, there is no gaseous evolution in the cell 24, as the gases are immediately dissolved in the solution. The presence of dissolved hydrogen from the cathode has no effect on the accuracy of the apparatus.

In Fig. 2, a detailed cross section of the absorption cells I5 and 33 is shown. Although the particular construction of the cell is not critical, the design shown is simple and has proven satisfactory. A barrel 5%, which in this case was a brass tube about 5 inches long and about inch diameter, is threaded on the ends to receiv correspondingly threaded bushings 5| and 52 which hold in place glass windows 53 and 54. The glass windows 53 and 54 are of the standard type used in saccharimeters and the like, and they are placed directly in contact with the ground ends of the barrel 50. Rubber gaskets 55 and 5B are used between the glass windows 53 and 54 and the bushings 5| and 52, respectively, to insure uniform pressure on the glass and leakproof joints. Near each end of the barrel 50 are inserted outlet and inlet tubes 51 and 58, which in this cell were inch copper tubing soldered to the barrel 50. The inlet tube 58 projects slightly into the barrel 50 and is closed at its end 59, there being provided an opening 60 for passage of solution. The opening 60 constituted a i e inch slit extending about one-third of the tubes circumference and positioned to face toward the opposite end of the barrel 50. The opening 63 was provided because it was found desirable to direct the stream of solution away from the window 54 so that any sediment in the solution would either settle out in the center of the barrel 50 or be swept away, thus reducing the frequency with which the windows must be cleaned.

In Fig. 3, a detailed cross section of the electrolysis cell 24 is shown. Obviously any kind of electroylsis cell may be used, provided the electrodes and container will not react with the alkaline solution passing through. However, the design shown is simple and inexpensive to construct, and is completely satisfactory. A container or cell body H3 is made of glass, and in the cell shown the body H! was blown from Pyrex glass tubing. The body 16 which is about 1.6 cm. in diameter, is provided with an inlet 'Il about 0.6 cm. in diameter and an outlet 12 about 0.7 cm. in diameter. A center portion 13 of the body 10 rises in the center to provide support for-an anode 14 which is made of platinum foil cemented to the portion 5 I3. oppositely disposed to the anode I4 is a cathode I5, also of platinum foil and cemented to the wall of the body I0.

In order to strengthen the body I the center portion I3 is filled with a resinous cement I0 which also serves as a support for conductors I1 and I0 imbedded therein. Thin platinum leads I9 and 80 are sealed through the body I0 and connect the anode I4 and cathode I with the conductors I1 and I8, respectively.

A fundamental problem in the design and operation of an apparatus of the type herein disclosed is that of delivering the concentrated, rather corrosive reagents at a constant rate within a minimum of space and equipment. A positive displacement pump is necessary for this purpose because the accuracy of the continuous analysis depends in large part on the metering of the reagents. A carefully machined gear pump may be satisfactorily used if it can be made of corrosion resistant materials. Due to the extremely corrosive nature of potassium hydroxide and pyrogallol it was found desirable to provide pumps of simple construction whose parts coming in com tact with reagent could be easily replaced. To this end a pump was designed which has no individual valves or ball check parts, but operates on the principle of a rotating notched piston which displaces a volume of the reagent solution by reciprocating motion, the notch, acting as the valve, rotating into a position opening the intake port on the start of the intake stroke and then into a position opening the discharge port and closing the intake port on the return stroke. The pump is shown in detail in Fig. 4.

Referring to Fig. 4, the complete pump comprises a housing A, driving means B, reciprocating means C and pump head D.

The pump head D comprises a casing I00 maehined to fit snugly in the end of the housing A. In order to prevent slippage of the casing I00, a set screw IOI is provided which looks the casing I00 in the pump housing A. A piston I02 passes through the center of the casing I00 and into a pump chamber I03. In order to provide an easily replaceable or interchangeable pump cylinder the casing I00 is bored to a larger diameter than the piston I02, at the end surrounding the chamber I03, and a cylinder I04 is snugly fitted therein. The exposed end of the cylinder I04 is closed by a screw plug I05 the end of which is machined to fit the cylinder wall to minimize leakage. In addition a gasket I05 is provided between the plug I05 and the cylinder I00. The casing I00 also contains two oppositely disposed bores I01 and I08 at right angles to the cylinder I05 and extending from the outside through the casing, and through corresponding holes in the cylinder wall, into the chamber I03. As shown, the bores I01 and I08 are the intake and exhaust ports of the pump, respectively. Also in the casing I00 a packing gland I09 is provided around the piston I02 to prevent leakage. The piston I02 contains a groove or fiat section I I0 extending across about one third of the circumference of the piston and long enough to appear before the bore III! on the intake stroke and (by rotation of the piston I02) to appear before the bore. I05 on the discharge stroke. In this way the piston performs the dual function of pumping the liquid and acting as intake and discharge valves.

The driving means B constitutes a worm gear II I which is driven by any standard means, such as an electric motor, and a gear I I2 meshing with the worm gear II I. Since the pump normally 0p- 6 erates at about sixty strokes per minute it is necessary to employ a large speed reduction in the gears III and H2, say 30.1, if the usual high speed electric motor is employed to run the pump. The gear H2 is slidably mounted on a shaft H3 but adapted to turn the shaft H3 by means of a spline H4, part of the gear H3 is seated in ball bearing H5 mounted in a casing H8, which supports the moving parts and takes up the thrust due to reciprocation of the pump. The shaft H3 is coupled to the piston I02 by means of a joint I I1. Also mounted in the casing I I0 is a packing gland H8 around the shaft H3 to prevent oil leakage.

The reciprocating means C comprises a cam H9, a spring I20 and a cam adjustment gear I2I. The cam H9 is rigidly mounted on the shaft H3 so that it turns therewith. A stationary member I22, which is mounted in the gear I2I and locked by a set screw I23, engages the cam H9 in an oblique plane so that, as the cam H9 rotates it is alternately moved away from and toward the member I22. In order to take up the lateral thrust of the cam H9 the shaft I I3 extends through the member I22 in which it moves freely.- The cam I I9 will always remain in contact with the member I22 by virtue of the compression spring I20, thus reciprocating the shaft H3 one complete stroke (i. e., forward and back again) for each revolution. 7

It is obvious that the rotation of the piston I02 and its reciprocation must be in a certain phase relationship in order for the section HIl'to face the bores I01 and I08 at the proper parts of the stroke, and in fact the capacity of the pump may be varied, within limits, by changing this phase relationship. This adjustment is the purpose of the gear I2I. The gear I2I meshes with a worm gear I24 mounted on a common shaft with a knob I25, so that by turning the knob I25 thegear I2 I, and thus the member I22, rotate to any desired position. In this Way the phase relationship between the rotation and reciprocation of the piston I02 may be altered or adjusted as desired. In order to hold the gear I2I in place and to take up the reaction of the spring I20 and the cam H9 a channel I26 which is fastened to the housing A passes across the back of the gear I2I. In the channel I26 a screw knob I21 is mounted so as to bear against the gear IZI for fine adjustment and to lock it against movement by accidental rotation of the knob I25. Proper lubrication of the pump is assured by placing oil in that part of the housing A which surrounds the driving and reciprocating means B and C, and for this purpose an oil hole and plug I 28 are provided.

An advantage of the pump described is that the parts most affected by the solution being pumped are extremely simple and few, and they may be easily replaced, or made of expensive materials at a minimum of cost. The chief location of corrosion has been the cylinder wall I04 and the piston. However, the effect of the solutions is slight if the cylinder and piston in the potassium hydroxide pump are made of Monel metal and in the pyrogallol pump of Durimet alloy (a chromenickel steel containing also molybdenum, silicon and copper). As an alternative the Durimet alloy may be replaced by 188 molybdenum steel.

As already indicated, the pump was designed to operate at about sixty strokes per minute, and at this speed the maximum capacity is about 0.6 cc. per minute.

In the apparatus described many variations are obvious. For example the mixing coils I1 and variations will be apparent to those skilled in 10 the art, and the invention should not be limited other than as defined by the appended claims.

The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

We claim:

Photometric apparatus for the continuous determination of dissolved oxygen in water and for calibrating its indications which comprises a first and second light absorption cell, means for fixing a predetermined flow of water to said first cell, an outlet conduit means from said first cell, including successively an inlet branch conduit, a mixing portion arranged to provide turbulent flow therein, an electrolyzing cell, a second inlet conduit, a second mixing portion to provide turbulent flow, an expanded portion to arrest turbulence, said outlet conduit then entering said second light absorption cell, light measuring means, including a light source and light responsive element, said light measuring means being mounted on a movable support and said cells being so positioned that said light measuring means can be shifted successively in light measuring arrangement with either of said cells, and an outlet from said second cell.

RICHARD L. TUVE. JOSEPH C. WHITE. ELMER L. LUKE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS I Date Number Name 820,113 Hinkson May 8, 1906 1,020,001 Van Pelt Mar. 12, 1912 1,159,699 Murdock Nov. 9, 1915 1,744,791 Nemetz Jan. 28, 1930 1,807,821 Behr June 2, 1931 1,919,858 Pettingill July 22, 1933 1,951,035 Parker n Mar. 13, 1934 1,954,925 Exton Apr. 17, 1934 1,960,615 Baker May 29, 1934 1,967,428 Quereau July 24, 1934 1,993,759 Stockmeyer May 12, 1935 2,007,871 Oldham July 9, 1935 2,114,234 Ornstein et a1 Apr. 12, 1938 2,118,837 Felton May 31, 1938 2,122,363 Christie June 28, 1938 2,238,903 Lieneweg Apr. 22, 1941 2,305,108 Rowe Dec. 15, 1942 OTHER REFERENCES Journal of Chemical Physics, June 1934, vol. 2, pp. 342-344.

Chemical & Metallurgical Engineering, July 1928, pp. 421-423. 

